Combined process for dyeing and finishing fabrics composed of cellulosic fibers

ABSTRACT

A PROCESS FOR EFFECTING THE DYEING AND FINISHING OF FABRICS OF CELLULOSIC FIBERS SIMULTANEOUSLY, WHICH COMPRISES APPLYING A LIQUOR CONTAINING AT LEAST ONE FINISHING AGENT SELECTED FROM THE GROUP CONSISTING OF TETRAOXANE AND PENTOXANE, AN ACID CATALYST, AND AT LEAST ONE DYESTUFF TO A FABRIC TO CELLULOSIC FIBERS, AND HEAT-TREATING THE FABRIC.

United States Patent Ofiice 3,679,348 Patented July 25, 1972 Int. (:1. D06}: 5/60,- D06m 9/00 U.S. Cl. 8-18 2 Claims ABSTRACT OF THE DISCLOSURE A process for effecting the dyeing and finishing of fabrics of cellulosic fibers simultaneously, which comprises applying a liquor containing at least one finishing agent selected from the group consisting of tetraoxane and pentoxane, an acid catalyst, and at least one dyestuff to a fabric of cellulosic fibers, and heat-treating the fabric.

This invention relates to the dyeing and finishing of fabrics of cellulosic fibers.

Heretofore, N-methylol compound such as urea-formaldehyde precondensate, melamine-formaldehyde precondensate, methylol ethyleneurea or dihydroxyethyleneurea have been mainly used for improving the crease resistance and wash-and-wear properties of cellulosic fabrics. When it is desired to subject the cellulosic woven fabrics simultaneously to the dyeing and modification finishing, it has been the general practice to dye the fabrics first and then subject the dyed fabrics to the finishing.

The main object of the present invention is to provide a process for dyeing, and improving the crease resistance and wash-and-wear properties of, cellulosic fabrics simultaneously, in view of the fact that the shorting of the finishing process is one of the economical and technical problems in the art of finishing fibers. Other objects of the invention will become apparent from the following description.

It has been found that these objects of the invention can be achieved by applying a dyestuff, and tetraoxane (i.e. cyclic tetraoxymethylene) and/or pentoxane, (i.e., cyclic pentaoxymethylene), which have not been used in the dyeing of finishing of fibers, simultaneously to fabrics of cellulosic fibers.

According to the present invention, there is provided a process for dyeing and finishing fibrics of cellulosic fibers which comprises applying a liquid containing at least one finishing agent selected from the group consisting of tetraoxane and pentoxane, an acid catalyst and at least one dyestutf selected from the group consisting of dyestuffs for cellulosic fibers, animal fibers, semisynthetic fibers and synthetic fibers to a fabric of cellulosic fibers, curing the treated fabric at a temperature higher than 100 C., and depending upon the dyestufl, subjecting the fabric to a known treatmnt for fixing the dyestuff in the cellulosic fabrics, thereby to obtain a cellulosic fabric which has been effectively dyed, and has superior crease resistance and wash-and-wear properties.

The tetraoxane or pentoxane used in the present invention is ring-opened by heating in the presence of an acid catalyst, and forms cross-linkages in the cellulose-molecules, which leads to the improvement of the crease resistance and wash-and-wear properties of the fabric. The tetraoxane or pentoxane may be used singly or as a mixture of these with each other, or as a mixture of either of these with trioxane (i.e., trioxymethylene). The trioxane, when used alone, presents difiiculty in the ringopening reaction and does not bring about sufficient modification and dyeing effects. The ring-opening reaction of trioxane proceeds considerably only when it is used in conjunction with tetraoxane or pentoxane, and gives effective finishing and dyeing.

The use of the afore-mentioned conventional N-methylol derivatives in place of the tetraoxane or pentoxane used in the invention cannot give dyeings having effective coloring and excellent crease resistance and wash-and-wear properties which can be obtained by the process of the present invention.

Other advantages of using tetraoxane or pentoxane or a mixture of these with each other for finishing of cellulosic fibers in the invention over the use of N-methylol derivatives are the soft feel of the finished cellulosic fabric, reduced tendency of the wash-and-wear properties of the fabric to degrade by washing, the substantial removal of operational difliculties incident to the generated of formaldehyde during the finishing treatment, and complete freedom from chlorine retention after finishing.

By the fabrics of cellulosic fibers, as used in the present invention, are meant fabrics made of fibers at least part of which consists of cellulosic fibers. The examples of the cellulosic fibers include natural fibers such as cotton and flux, the staples and filaments of regenerated fibers such as w'scose rayon, cupra-rayon and polynosic fibers, and blends of these cellulosic fibers with the staples or filaments of polyester fibers, polyacrylic fibers, polyamide fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, polyolefinic fibers, cellulose ester fibers, silk, wool and glass fibers.

The dyestuffs for cellulosic fibers which can be used in the process of the present invention may be any dyestuffs such as direct dyestuffs, fluorescent brightening agents, vat dyestuffs and reactive dyestufis which can form a homogeneous solution or dispersion as mixed with at least one of tetraoxane and pentoxane and an acid catalyst.

The vat dyes used in the invention are mixed with surface active agents and pulverized superior to use, and need be dispersed in the pigment state in a liquor containing tetraoxane, pentoxane or a mixture of these and an acid catalyst.

The preferred reactive dyestuffs are those which react with, and dye, cellulosic fibers by heating in the presence of an alkaline or acid catalyst. Examples of these reactive dyestuffs reactive in the presence of an alkaline catalyst are those having at least one of monochloroor dichloro-s-triazine groups, dichloroor trichloro pyrimidine groups, dichloroquinoxaline groups, or vinyl sulfone groups as the reactive group. As those reactive dyestuffs which are reactive in the presence of an acid catalyst, there have been known dyestuffs having at least one of active hydroxymethyl groups, such as active hydroxymethylamino, bishydroxymethylamino or lower alkoxymethylamino groups bound to a triazine ring (Japanese patent publication No. 23,736/ 61) and those having active methoxymethyl groups bound to the nitrogen or oxygen atom (Japanese patent publication No. 17,149/ 66).

Reactive dyestuffs of the type which does not react directly with fibers but is bound to the fibers by a covalent bond through a cross-linking agent can also be used for application to the cellulosic woven fabrics in accordance with the process of the present invention. The dyestuffs which come within this type are described in German Patent 1,155,088 which discloses that a dyestuif having a hydroxyl or amino group capable of reacting with an acryloyl group is applied to cellulosic fibers together with an alkaline agent and a polyfunctional cross-linking agent represented by N,N',N-triacry1ols hexahydrotriazine,

r the treated fibers are dyeing. One of such type of reactive dyestuffs which has an active hydrogen capable of reacting with methylol compounds in the presence of an acid catalyst but has no afinity for cellulosic fibers is especially preferred in the process of the invention. The dyestuff of this kind form a -firm methylene cross-linkage between cellulosic fibers by heating together with a methylol compound and an acidcatalyst. To this end, there can be used dyestuffs in which the dyestulf molecules'have at least one of free hydroxylprimary or secondary amino groups, or aromatic carbon atoms whose reactivity have been increased by these groups. Of these, dyestuffs having a hydroxyl or amino group linked to the chromophore group through an aliphatic side-chain or an imino group which constitutes a component of heterocyclic rings exhibit superior dyeability. As the chromophore group, ordinary dyestufi. residues such as azo, anthraquinone, phthalocyanine, nitro, triphenylmethane and azine can be used,

and the chromophore group is not restricted to particular compounds. For exhibiting good dyeability, the dyestufis should have at least one of electropositive groups having suflicient activity (e.g., hydroxyl, amino imono group), and be well soluble in a solvent for forming a dyeing and finishing liquor. In a dispersed state, the dyestuffs cannot be expected to give good results. Hence,

when water is used as a solvent, it is necessary that at to cellulosic fibers together with tetraoxane or pentoxane and an acid catalyst and heated to a temperature above 100' C., the ring-opened tetraoxane or pentoxane reacts with the active hydrogen atoms in the dyestuflf, and the dyestuff is firmly linked to the fibers via the polyoxymethylene bridge. In this manner, a dyestufi which by itself has no afiinity with cellulose dyes cellulosic fibers fast. At the time, the cross-linking of the cellulosic fibers by tetraoxane or pentoxane proceeds, and gives superior crease resistance and wash-and-wear properties.

- Where the woven fabrics of cellulosic fibers are fabrics of a blend of cellulosic fibers and other fibers, dyestuffs for the latter fibers are also applicable conjointly with the above-mentioned dyestuffs for cellulosic fibers. For some purposes, only the dyestuffswhichdye the partner fibers blended with 'cellulosics especially disperse dyes are used. In this case, the cellulosic fibers in the blend isnot dyed, and only the other components are dyed. Sumcient dyeing efiect is obtainedfrequently with this procedure in the case of pale dyeing and fluorescent brightemng.

These dyestuffs may be those which are capable of forming a homogeneous solution or dispersion when mixed with the finishing agent together with the dyestufl for cellulosic fibers. As the dyestuffs suited for this object, there can be named dyestufis for animal fibers, semisynthetic fibers and synthetic fibers, the examples of the first one being acid dyes and metallized dyes, and the examples of the last two being disperse dyes.

-In order to prepare a liquor comprising at least one finishing agent selected from the group consisting of tetr'aoxane and pentoxane, an acid catalyst and a dyestutf of the described types, water or a mixture of water with a water-miscible organic solvent is used. Such organic solvents include, for instance, alcohols such as methanol and ethanol, ethers such as dioxane, and ketones such as acetone, methyl ethyl ketone. The amount of tetraoxane or pentoxane to be added to the liquor varies depending upon the degree of crease resistance required, but generally 0.1-10 parts by. weight per 100 parts of the liquor.

i The acid catalyst used in the process of the present heated thereby to. effect the invention may be any catalyst which exhibits acidity in the heat-treatment above 1 00 C., the examples being inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, organic acids such as formic acid, acetic acid, oxalic acid, benunesulfonic acid, and phytic acid, ammonium salts or amine salts thereof, and metal salts such as magnesium chloride, zinc nitrate, zinc chloride, aluminium sulfate, magnesium borofluoride and zinc borofiuoride. At least one of these compounds is used as the acid catalyst in the process of the present invention.

When the liquor comprising the aforementioned finishing agent, dyestuflf and acid catalyst is incorporated in a fabric of cellulosic fibers, the liquor may contain assistants conventionally used for the finishing of cellulosic fabrics, such as softening agents, water repellents, antistatic agents, wetting agents and pH control agents in dissolved or dispersed state.

Application of the liquor comprising the finishing agent, acid catalyst and dyestuff to fabrics of cellulosic fibers may be carried out by immersing the fabrics in the liquor and then squeezing them by a padding mangle; or by at a temperature in the range of 130-180 C., and for a woven fabric made of a blend of polyester fibers and cellulosic fibers, a temperature in the range of 180-230" C.

In 'view of adverse effects that might be exerted on the cellulosic fibers, such as discoloration and fall in strength,

. this curing might better be performed at a temperature lower than 230 C. for practical purposes.

The ring of tetraoxane or pentoxane opens upon curing by the action of an acid catalyst, and cross-linkage is formed among the molecules of cellulose, thereby giving good crease resistance and wash-and-wear properties to the cellulosic fibers.

When a fabric made of a blend of polyester fibers and cotton is treated with a treating liquor containing a disperse dye, its curing gives an additional effect of dyeing the polyester fibers with the disperse dye in addition to the above-mentioned effects. In this case, with N-methylol resins, the absorption of the dyestuffs to the fibers, especially to polyester fiber, is hindered by resin finishing, and only pale colors are obtained. Furthermore, the treated fibers have considerably lower fastness to light, and rubbing. However, by using tetraoxane, pentoxane or a mixture of these in accordance with the process of the present invention, dyeings having good fastness can be obtained.

When a reactive dyestuif reactive in the presence of an alkaline catalyst is used for dyeing cellulosic fibers, it is necessary to apply an alkaline aqueous solution to the cellulosic fabric after curing, and then heating it by dry heat or by steam to a temperature above C., preferably -150 C. This treatment results in a covalent bond between the reactive dyestuff and the cellulosic fibers. By the term alkaline aqueous solution used herein is meant an aqueous solution which shows substantial alkalinity and contains hydroxide, carbonate, bicarbonate, phosphate or silicate of sodium or potassium.

When the reactive dyestuff described in German Pat. No. 1,155,088 which will react with a cross-linking agent in the presence of an alkaline catalyst is used, first a dyestulf, a cross-linking agent, a finishing agent, and an acid catalyst are mixed, and the mixture as liquid is applied to a cellulosic fabric. The treated fabric is then heat-treated to form cross-linkage between the cellulosic fibers by tetraoxane and/or pentoxane, and then treated with alkali to effect the dyeing. The cross-linking agent for the dyestuff does not change much by heating together with the acid catalyst, and the alkali treatment will result in the bonding of the dyestulf and the fibers.

When dyestuffs reactive in the presence of an acid catalyst and those which form cross-linkage with methylol compounds are employed, only the curing procedure can lead to cross-linking and dyeing of the fibers simultaneously, and no post-treatment is necessary.

When a vat dye is used for dyeing cellulose fibers, it is necessary that an alkaline aqueous solution containing a reducing agent be applied to the cellulosic fabric after curing, and the treated fabric is then heat-treated at a temperature above 80 C., preferably 100-110 C. By the reducing agent is meant reducing agents generally used in the dyeing with vat dyes, such as sodium hydrosulfite, zinc hydrosulfite, formaldehyde-sodium sulfoxylate, or formaldehyde-zinc sulfoxylate. The vat dye is reduced with the alkaline chemical, reducing agent and heat-treatment to a leuco salt. After heat-treatment, the leuco salt is oxidized in air, or with oxygen in water or if necessary, with an oxidizing agent such as hydrogen peroxide, and firmly fixed with the cellulosic fibers.

The invention will further be described specifically with reefrence to the following examples, in which all parts and percentages are by weight.

EXAMPLE 1 A scoured and bleached cotton broad cloth of 40 count was immersed in 100 parts of a liquor containing 1 part of Celmazol Red B (CJI. Reactive Red 22; Mitsui Toatsu Chemicals, Inc., Japan), 3 parts of tetraoxane and 1 part of zinc nitrate hexahydrate, and squeezed to 70% pickup. The treated cloth was introduced into a hot-flue dryer and dried for minutes at 100 C., followed by curing for 3 minutes at 150 C. The cured cloth was then immersed in 100 parts of an aqueous solution containing 0.6 part of sodium hydroxide, 25 parts of anhydrous Glaubers salt and 0.5 part of sodium metanitrobenzenesulfonate, and squeezed with a padding mangle to a pick-up of 80%. The cloth was then introduced immediately into a steamer, and steamed for 30 seconds at 102 C. The cloth'was immersed in a 0.2% aqueous solution of glacial acetic acid, and soaped with Monogen (surface active agent; Daiichi Kogyo Seiyaku Co., Ltd., Japan) for minutes at 100 C. The cloth was dyed in brilliant red, and had superior crease resistance and wash-and-wear properties.

The crease resistance of the treated cloth was measured by the Monsanto method (AATCC, 66-1968). As a measure for the degree of coloring, the spectral reflectance curve of visible region of the dyed cloth towards a white plate of aluminum oxide was measured by an automatic spectrophotometer EPR-2 (product of Hitachi, Limited, Japan), and the tristimulus values were calculated in accordance with the method of I18 Z 8722-1966).

The crease recovery angle of the dyed cloth was 272, and the tristimulus value was 26:33.60, Y=23.22 and Z=23.73. In contrast, the crease recovery angle of the non-treated cloth was found to be 178.

EXAMPLE 2 One hundred parts of a liquor containing 2 parts of Mikethren Yellow 4GF Super Fine (Cl. Vat Yellow 20, finely dispersed vat dye produced by Mitsui Toatsu Chemicals, Inc., Japan), 3 parts of tetraoxane and 3 parts of magnesium chloride trihydrate are prepared. A scoured and bleached cotton broadcloth of '40 count was i-mmersed in the resulting liquor, squeezed in the same way as set forth in Example 1, and then dried.

The dried cloth was cured for one minute at 170 C., then immersed in an aqueous solution comprising 4 parts of sodium hydroxide, 4 parts of hydrosulfite and 3 parts of anhydrous Glaubers salt at 25 C., and squeezed to 90% pick-up. The treated cloth was immediately introduced into a steamer, and steamed for 30 seconds at 102 C. The cloth was then Washed with water, oxidized in 0.2% aqueous hydrogen peroxide, and then soaped for 10 minutes at 100 C. in an aqueous 0.3% solution of 6 Marseilles soap to give a dyed cotton cloth having excellent crease resistance and wash-and-wear properties.

For comparative purposes, a cotton broad cloth of 40 count was subjected to the same treatment as set forth above except that instead of 3 parts of the tetraoxane, 10 parts of Uramine T-447 (finishing agent of dihydroxy ethylene urea type, product of Mitsui Toatsu Chemicals, Inc., Japan).

The crease recovery angle and tristimulus values of these two types of cotton cloths were measured, and the results are given in the following table. It is seen from these results that better crease resistance and deeper color can be obtained with the use of tetraoxane than with the use of Uramine T-447.

One hundred parts of a liquor containing 2 parts of Mikethrene Blue RSN Super Fine (C.I. Vat Blue 4; finely dispersed vat dye, product of Mitsui Toatsu Chemicals, Inc., Japan); one part of Miteton Polyester Blue BLN (C.I. Disperse Blue 105, disperse dye, product of Mitsui Toatsu Chemicals, Inc., Japan), 3 parts of pentoxane and 2 parts of zinc nitrate hexahydrate was prepared.

A scoured and bleached 44 count polyester-cotton blended fabric 65/ 35) was immersed in the above liquor, and squeezed by a padding mangle until the wet pick-up of the cloth reached 65%. The treated cloth was dried, cured, padded with an alkaline solution containing a reducing agent, steamed, and other necessary treatments in the same way as set forth in Example 2 to give a blue dyeing.

The dyed cloth had a crease recovery angle of 306, and its tristimulus values were X=15.73, Y=15.20 and Z=38.05.

EXAMPLE 4 A scoured and bleached broad cloth of 40-count polyester-cotton blend was immersed in 100 parts of a liquor comprising 2 parts of Miketon Polyester Pink BL (01. Disperse Red 55, disperse dye produced by Mitsui Toatsu Chemicals, Inc., Japan), 2 parts of Mikethrene Red FFB Super Fine (C.I. Vat Red I10; finely dispersed vat dye produced by Mitsui Toatsu Chemicals, Inc., Japan), 4

parts of pentoxane and 1 part of zinc chloride trihydrate,

and squeezed to 70% pickup. The treated cloth was introduced into a hot-flue dryer, dryed for 5 minutes at 100 C., and then cured for seconds at 200 C. The cured cloth was immersed in parts of an aqueous solution comprising 4 parts of sodium hydroxide, 4 parts of hydrosulfite and 3 parts of anhydrous Glaubers salt, and squeezed to 80% pickup. Immediately thereafter, the cloth was introduced into a steamer, and steamed for 30 seconds at 102 C. The cloth was washed with water, oxidized in 0.2% aqueous hydrogen peroxide, and soaped for 10 minutes at 100 C. in an aqueous 0.3% Monogen (surfactant, product of Daiichi Kogyo Seiyaku Company, Ltd., Japan) to give a brilliant red dyeing which had excellent crease resistance and wash-and-wear properties.

EXAMPLE 5 A scoured and bleached cotton broad cloth of 40 count was immersed in 100 parts of a liquor comprising 0.5 part of Mitsui Direct Sky Blue 5B (C.I. Direct Blue 15; direct dye produced by Mitsui Toatsu Chemicals, Inc., Japan), 3 parts of pentoxane and 1 part of zinc nitrate hexahydrate, and squeezed to 65% pick-up. The treated cloth was introduced into a hot-flue dryer, and dried for 5 minutes at 100 C. The cloth was cured for 60 seconds at 7 170 C., 'and soaped for 10 minutes at 60 C. In an aqueous solution comprising 0.3% of Marseilles soap. A blue EXAMPLE 6 Armored and bleached cotton broad cloth of 40 count was immersed in 100 parts of a liquor comprising 2 parts of Suprazo Red 4B (0.1. Direct Red 81; fast direct dye produced by -Mitsui Toatsu Chemicals, Inc., Japan), 4 parts of tetraoxane and 2 parts of magnesium chloride hexahydrate, andsq-ueezed to 65% pickup. The treated cloth was introduced into a hot-blue dryer, and dried for 5 minutes at 100 C. The cloth was cured for 90 seconds at 160 C., subsequently steamed for 3 minutes at 102 C., and soaped for minutes at 60 C. in an aqueous solution containing 0.3% of Monogen (surfactant, produced by Daiichi Kogyo Seiyaku Company, Ltd., Japan). A red dyeing having excellent crease resistance and washand-wear properties was obtained.

7 EXAMPLE 7 A scoured and bleached 40 count polyester-cotton blended, cloth was immersed in 100 parts of a liquor comprising 2 parts of Miketon Polyester Yellow YL (C.I. Disperse Yellow '42; disperse dye produced by Mitsui Toatsu Chemicals, Inc., Japan), 2 parts of Celmazol Yellow GN (reactive dyestufl? reactive in the presence of an alkaline vcatalyst; product of Mitsui Toatsu Chemicals,

Inc., Japan), 4 parts of tetraoxane and 1 part of magnesium chloride .hexahydrate, and squeezed to a pick-up of 70%. The cloth was introduced into a hot-flue dryer, and dried for 5 minutes at 100 C., and then cured for 90 minutes at 200 C. The cured cloth was immersed in 100 parts of an aqueous solution comprising 0.6 part of sodium hydroxide, 25 parts of anhydrous Glaubers salt andv 0.5 part of sodium metanitrobenzenesulfonate, and squeezed to 80% pick-up. Immediately thereaftenthe cloth was introduced into a steamer and steamed for 30 seconds at 102 C. The cloth was further immersed in an aqueous 0.2% solution of glacial acetic acid, and soaped for 10 minutesat 100 C. in a 0.3% aqueous solution ofMonogen (surfactant; product of Daiichi Kogyo Seiyaku Company, Ltd., Japan). A brilliant yellow dyeing of polyester-cotton blend cloth having excellent crease resistance and wash and-wear properties was obtained.

EXAMPLE 8 v A scoured and bleached cotton-polyester blend broad cloth of 40 count was immersed in 100 parts of a liquor comprising 2 parts of Miketon Polyester Blue TGSP conc. (disperse dye produced by Mitsui Toatsu Chemicals, Inc., Japan), 2 parts of Celmazol Brilliant Blue R (C.I. Reactive Blue 19; reactive dyestufi reactive in the presence of an alkaline catalyst, produced by Mitsui Toatsu Chemicals, Inc., Japan), 4 parts of tetraoxane and 1 part of magnesiumjchloride hexahydrate, and squeezed to 70% pick-up. 'Ihetreated cloth was introduced into a hot-flue dryer and dried for 5 minutes at 100 C. The cloth was then cured for 60 minutes at 220 C. Thereafter, the cloth was immersed in 100 parts of an aqueous solution comprising 0.6 part of sodium hydroxide, 25 parts of anhydrous Glaubers salt and 0.5 part of sodium metanitrobenzenesulfonate, and squeezed to a pick-up of 80%. Immediately thereaftenthe cloth was baked for one minute at 190 C., and then immersed in a 0.2% aqueous solution of glacial acetic acid. Thereafter, the cloth was soaped for 10 minutes at 100C. in a 0.3% aqueous solution of Monogen (surfactant; product of Daiichi Kogyo Seiyaku Company, Ltd., Japan) to give a blue dyeing of polyestereotton blend cloth having excellent crease resistance and wash-and-wear properties.

v EXAMPLE 9 A scoured and bleached 40-count polyester cotton broad cloth was immersed in 100 parts of a liquor comprising 2 parts of Miketon Polyester Red P3 (0.1. Disperse Red 60;

glacial acetic acid, and soaped for 10 minutes at 100' C. V in a 0.3% aqueous solution of Monogen (surfactant, produced by Daiichi Kogyo Seiyaku Company, Ltd., Japan) to give a brilliant red dyeing of polyester-cotton blend cloth having excellent crease resistance and wash-andwear properties.

EXAMPLE 10 A 40-count broad cloth of a blend of polyester fibers and cotton, which had been scoured and bleached, was 1 immersed in 100 parts of a liquor comprising 2 parts of Miketon Polyester Red PB (G1. Disperse Red 60, disperse dye produced by Mitsui Toatsu Chemicals, Inc., Japan, 2 parts of Procion Brilliant Red H3BN (C.E. Reactive Red 29; reactive dyestuif reactive in the presence of an alkaline catalyst, produced by Imperial Chemical Industries, Great Britain), 3 parts of tetraoxane and 1.5 parts of zinc borofluoride, and squeezed, dried, cured, padded with alkali in the same way set forth in Example 7. The treated cloth was squeezed to pick-up. Immediately thereafter, the cloth was introduced into a steamer, and steamed for 60 minutes at 102 C. The cloth was then immersed in a 0.2% aqueous solution of glacial acetic acid, and soaped in an aqueous 0.3% solution of Monogen (surfactant, produced by Daiichi Kogyo Seiyaku Company, Ltd., Japan) for 10 minutes at C. to give a brilliant red dyeing of polyester-cotton blend cloth having excellent crease resistance.

EXAMPLE l1 A second and bleached cotton broadcloth of 40 count was immersed in 100 parts of a liquor comprising 2 parts of Basasol Red Brown RL (reactive dyestufi reactive through a cross-linking agent; product of BASF, Germany), one part of a Fixing Agent P (cross-linking agent, product of BASF, Germany), 4 parts of tetraoxane benzenesulfonate, and squeezed to a pick-up'of 80%..

Immediately thereafter, the cloth was introduced into a steamer, and steamed for 30'seconds at 102 C. The

steamed cloth was immersed in an aqueous 0.2% solu-.

tion of glacial acetic acid, and soaped for 10 minutes at 100 C. in a 0.3% aqueous solution of Monogen (sur- I factant; product of Daiichi Kogyo Seiyaku Company, Ltd., Japan) to give an orange-brown dyeing of cotton cloth having excellent crease resistance and wash-and wear properties.

.EXAMPLE 12 A secured and bleached cotton broad cloth of 40 count was immersed in 100 parts of a liquor comprising '1 part of Calcobond Red 33 (reactive dyestufi reactive in the presence of an acid catalyst, product of American Cyanamid Company, U.S.A.), 3 parts of tetraoxane and 1.5 parts of magnesium chloride hexahydrate, and squeezed to 70% pick-up. The treated cloth was introduced into a hot-flue dryer, and dried for 5 minutes at 100" C, and then cured for one minute at C. The

cloth was then soaped for 10 minutes at 100 C. in an aqueous 0.3% solution of Monogen (surfactant, product of Daiichi Kegyo Seiyaku Company, Ltd., Japan) to give a brilliant deep red dyeing of cotton broad cloth which had excellent softness, crease resistance, wash-and-wear properties, and color fastness, as well as shown in the following table.

These properties were measured by the following methods.

Crease resistance: Crease recovery angle measured by the Monsanto method.

Softness: Total hand measured by the handrometer method.

K/S value (Kubellca-Munk Function): Spectral reflectance curve of visible region of the dyed cloth towards a white plate of aluminium oxide is measured by an automatic spectrophotometer EPR-2 (product of Hitachi Limited, Japan), and the K/S value is calculated from the minimum value (R) of the reflectance. This value is a measure of the strength of the dyed cloth.

Fastness to light: Measured according to JIS L-1044 (1959).

For comparative purposes, the foregoing experiment was repeated in the same way as set forth above except that (1) tetraoxane was not used, (2) 12 parts of a dihydroxyethylene urea type finishing agent (Uramine T-447, product of Mitsui Toatsu Chemicals, Inc., Japan) was used instead of 3 parts of the tetraoxane, and (3) 15 parts of a propylene urea type finishing agent (Uramine T-926, product of Mitsui Toatsu Chemicals, Inc., Japan) was used instead of 3 parts of the tetraoxane.

Crease recovery Light softness angle 1 fastness Finishing agent (deg) Kl S (class) None 40 17 5 6. 6 3-4 Tetraoxane 41 298 6. 7 34 Urarm'ne T-447. 48 291 6. 1 2 Uramine T-926 46 290 5. 1 2

! Crease resistance.

It is seen from the above table that according to the process of the present invention, dyeings of superior softness, crease resistance, color strength and light fastness can be obtained than by using the known finishing agents.

EXAMPLE 13 A scoured and bleached 40-count polyester-cotton blended broad cloth was immersed in 100 parts of a liquor comprising 1 part of Calcobond Scarlet Y (reactive dyestulf reactive in the presence of an acid catalyst, product of American Cyanamid Company, U.S.A.), 2 parts of Miketon Polyester Scarlet BRSF (disperse dyestuff, product of Mitsui Toatsu Chemicals, Inc., Japan), 3 parts of tetraoxane and 1.5 parts of magnesium chloride hexachloride, and squeezed to a pick-up of 70%. The treated cloth was introduced into a hot-flue dryer, and dried for 5 minutes at 100 C., and then cured for 90 seconds at 200 C. The cloth was soaped for minutes at 80 C. in an aqueous solution containing 0.2% hydrosulfite, 0.2% 0.2% sodium hydroxide, and 0.2% Scourol 400 (surfactant, produced by Kao Soap Company, Ltd.,

Japan) to give a brilliant red dyeing of polyester-cotton blend cloth, which had excellent softness, crease resistance, wash-and-wear preperties and color fastness.

EXAMPLE 15 A scoured and bleached 40-count polyester-cotton blended broad cloth was immersed in 100 parts of a liquor comprising 2 pants of Calcobond Blue B (reactive dyestufl reactive in the presence of an acid catalyst, product of American Cyanamid Company, U.S.A.), 2 parts of Miketon Polyester Blue TGSF conc. (disperse dye, product of Mitsui Toatsu Chemicals, Inc., Japan), 3 parts of tetraoxane and 1.5 parts of magnesium chloride hexahydrate, and equeezed to 70% pick-up. The treated cloth was introduced into a hot-flue dryer, and dried for 5 minutes at 100 C., and then cured for one minute at 220 C. The cured cloth was soaped for 10 minutes at C. in an aqueous solution comprising 0.2% hydrosulfite, 0.2% sodium hydroxide and 0.2% Scourol 400 (surfactant, product of Kao Soap Company, Ltd., Japan) to give a brilliant blue dyeing of polyester-cotton blend cloth, which had excellent softness, crease resistance, wash-and-wear properties and color fastness.

EXAMPLE 16 A scoured and bleached cloth of 50/50 nylon-rayon staple blend was immersed in 100 parts of a liquor comprising 2 parts of Mitsui Acid Milling Red FG (C.I. Acid Red 276, acid dye produced by Mitsui Toatsu Chemicals, Inc., Japan), 2 parts of Calcobond Red 3B (reactive dyestufl reactive in the presence of an acid catalyst, product of American Cyanamid Company, U.S.A.), 4 parts of tetraoxane and 2 parts of magnesium chloride hexahydrate, and squeezed to 70% pick-up. The treated cloth was introduced into a hot-flue dryer, and dried for 5 minutes at 100 C., and then cured for seconds at 160 C. The cured cloth was soaped for 10 minutes at 60 C. in an aqueous solution of 0.3% Monogen (surfactant, product of Daiichi Kogyo Seiyaku Company, Ltd., Japan) to give a brilliant red dyeing of the nylonrayon blend cloth, which had excellent crease resistance and wash-and-wear properties.

EXAMPLE 17 A scoured and bleached cotton broad cloth of 40 count was immersed in parts of a liquor comprising a solution in water of 0.1 part of Mikephor RFA conc. (C.I. Fluorescent Brightening Agent 176; fluorescent brightening agent for cotton, product of Mitsui Toatsu Chemicals, Inc., Japan), 4 parts of tetraoxane and 1 part of zinc nitrate hexahydrate, and squeezed to a pick-up of 65% The treated cloth was introduced into a hot-flue dryer, and dried for 5 minutes at 100 C., and then cured for 3 minutes at C. The cured cloth was soaped for 10 minutes at 50 C. in an aqueous solution comprising 0.2 part of Monogen (surface active agent, product of Daiichi Kogyo Seiyaku Company, Ltd., Japan) and 0.2 part of soda ash, washed with water at 4050 C., and then dried. The resulting cloth was well whitened, and had excellent softness, crease resistance, and wash-and-wear properties.

EXAMPLE 18 A broad cloth of 40 count made of a blend of polyester and cotton was immersed in 100 parts of a liquor comprising 3 parts of Mikephor ETN conc. (a fluorescent brightening agent for polyesters, product of Mitsui Toatsu Chemicals, Inc., Japan), 4 parts of tetraoxane and 1 part of magnesium chloride hexahydrate, and squeezed to 65% pick-up. The treated cloth was dried for 5 minutes at 100 C. in a hot air dryer, and cured for 60 seconds at C. The cured cloth was soaped for 10 minutes at 70 C. in an aqueous solution of 0.2% Monogen (surfactant, product of Daiichi Kogyo Seiyaku Company, Ltd., Japan). The resulting cloth was well whitened and had excellent softness, crease resistance and wash-and-wear properties.

1 1 EXAMPLE 19 A scoured and bleached 40-count broad cloth of a blend of polyester and cotton was immersed in 100 parts of a liquor comprising 0.1 part of Mikephor RFB cone. (a fluorescent brightening agent for cotton, product of Mitsui Toatsu Chemicals, Inc., Japan), 2 parts of Mikephor ETN and 0.2 part of soda ash, washed with water at 4050 C.,

and dried. The resulting cloth was well whitened and had excellent softness, crease resistance and wash-and-wear properties.

EXAMPLE 20 A scoured and bleached cotton broad cloth of 40 count was immersed in 100 parts of a liquor comprising one part of the monoazo dyestuflE expressed by the foregoing formula, 3 parts of tetraoxane and 2 parts of magnesium chloride hexahydrate, and squeezed to 70% pick-up. The treated cloth was introduced into a hot-flue dryer, and dried at 100 C. for 5 minutes, and then cured for 1 minute at 170 C. The cured cloth was soaped for minutes at 100 C. ina 0.3% aqueous solution of Monogen (surfactant produced by Daiichi Kogyo Seiyaku Company, Ltd., Japan) to give a brilliant yellow dyeing (the spectrophotometric reflectant measurement of the dyed cloth resulted in the, minimum reflectance of 9.2% at 400 m When the dyed cloth was boiled for 30 minutes in pyridine, thedecoloration of the dyed cloth was not observed. The color fastness characteristics of the dyed cloth were as follows: fastness to light-class 5 (HS L 1044- 1959); fastness to washing, alteration in colorclass 4, nylon stainingclass 5; and wool stainingclass 5 (HS L 1045-1959, MC-3 method). The dyed cloth, on the other hand, had a crease recovery angle of 268 (nontreated cloth having a crease recovery angle of 173 0.). Furthermore, the finished cloth had'good handle.

EXAMPLE 21 SO NB NH-QCHmmOH A scoured and bleached 40-count polyester-cotton blended broad cloth was immersed in 100 parts of a liquor comprising 0.5 part of the dyestulf of the foregoing formula, 3 parts of pentoxane and 1 part of zinc nitrate hexahydrate, and squeezed, dried, cured and soaped in the same way as set forth in Example to give a brilliant blue dyeing having good handle, which had a crease recovery angle of 307 (non-treated cloth having a crease recovery angle of 274).

EXAMPLE 22 A scoured and bleached 40-count broad cloth of a blend of polyester and cotton was immersed in parts of a liquor comprising 1 part of the dyestulf of the above formula, 1.5 parts of trioxane, 1.5 parts of tetra- CHsC H1 11 CHaC H 011 oxane and 3 parts of magnesium chloride hexahydrate, and treated in the same way as set forth in Example 20 to give a reddish-yellow dyeing having good fastness to washing.

The procedure of Example 22 was repeated using the dyestutf of the above formula instead of the dyestufi of Example 22. A finished cloth dyed in orange was obtained.

EXAMPLES 24-26 The procedure of Example 20 was repeated using each of the following dyestuffs instead of the dyestufi of Example 20. Finished cloths have the respective color indicated below were obtained.

Example number HaC Grumman),

We claim:

1. A process for effecting the dyeing and finishing of fabrics of cellulosic fibers simultaneously, which comprises applying a liquor containing at least one finishing agent selected from the group consisting of tetraoxane and pentoxane, an acid catalyst, and at least one dyestufl to a fabric of cellulosic fibers, and heat-treating the fabric.

2. A process for effecting the dyeing and finishing of fabrics of cellulosic fibers simultaneously, which comprises applying a liquor containing at least one finishing agent selected from the group consisting of tetraoxane and pentoxane, an acid catalyst, and at least one dyestufi to a fabric of cellulosic fibers, heat-treating the fabric,

and subjecting the heat-treated fabric to a known treatment for fixing the dyestuff to the fabric.

References Cited Anon., Chemical and Engineering News, June 15, 1970, pp. 4647.

GEORGE F. LESME S, Primary Examiner J. CANNON, Assistant Examiner U.S. Cl. X.R.

8-1R,1D,1E,1G,1T,lUA,1W,21R,21A, 21 B, 21 C, 21 D, 22, 24, 34, 35, 36, 57, 61, 74, 115.7, 116.4, 127.6, 115.5, 129 

